A brief overview of the present status of the mechanisms involved in electrospray mass spectrometry.

A brief account of the mechanisms by which ions in solution are converted to ions in the gas phase is given on the basis of information available in the literature and the four companion articles on electrospray mass spectrometry (ESMS) in this issue. The following stages/phenomena are described: (a) production of the charged droplets at the ES capillary tip; (b) evolution of the charged droplets due to solvent evaporation and droplet fission caused by Coulombic repulsion of the charges on the droplets; production of the gas phase ion from very small charged droplets by the charge residue model (CRM) or the ion evaporation method (IEM); (c) dependence of the sensitivity in ESMS on the chemical nature of the analyte and its concentration as well as on the concentration of other electrolytes that are present in the solution; qualitative predictions on the sensitivity of the analyte based on the surface activity of the analyte ions; (d) relationship between ions produced in the gas phase and original ions present in the solution; and (e) globular proteins. Much of the information presented in (a)-(e) has been available for some time in the literature. However some significant advances are relatively recent. Recent results by de la Mora and co-workers, including their contribution in this Special Feature, provide very strong evidence that small ions (in distinction from macroions such as bio-macroions) are produced by IEM. On the other hand, macroions and particularly the polyprotonated globular proteins are produced by CRM. Also noteworthy is the development of an equation by Enke with which the observed relative ion signal intensities of the gas-phase ions produced can be predicted on the basis of the ion concentration in solution over a wide concentration range. The recognition that the sensitivity of organic analyte ions can be qualitatively predicted on the basis of the hydrophilicity or hydrophobicity of the part of the molecule that is not part of the charged (ionic) group and affects the surface activity of the ionic species is also noteworthy and a very useful relatively recent development. Copyright 2000 John Wiley & Sons, Ltd.